Crotonic acid ester of polyhydric alcohol



Patented Apr. 23, 1940 UNITED. STATES 'amas'za cao'romo ACID ss'rsa or rotmnmc HOL Y Herman A. Bruson, Philadelphia, Pa., assignor to Biihm 8; Haas Company, Philadelphia, Pa.

No Drawing. Original application August 23,

1933, Serial No. 686,443. Divided and this appllcation September 23, 1938, Serial No. 231,329

7 Claims.

This invention relates to plasticizers for organic plastic substances and resinous material; and more particularly to plasticizers for cellulosic derivatives, such as cellulose esters and cellulose ethers, especially nitrocellulose and acetyl cellulose; and deals more specifically with the plasticizing of such resinous materials by incorporating intimately therewith a purified, vacuum-distilled polyhydric aliphatic alcohol ester 10 of crotonic acid or an air-blown derivative thereof.

It is already known that a great many high boiling esters of organic acids are useful as plasticizers for cellulosic derivatives. In fact,

practically all known esters of organic acids are compatible with nitrocellulose to a more or less degree and are capable of giving clearfilms therewith. Relatively few esters, however, are compatible with cellulose acetate, especially if such esters are high boiling liquids; the majority of the well known plasticizers such as castor oil,

dibutyl phthalate, tricresylphosphate and the like being incompatible with cellulose acetate (except in very small amounts) and therefore useless therein as plasticizers since they produce unhomogeneous or turbid films.

It is also known that the esters of the lower fatty acids with polyhydric alcohols such as triacetin and tributyrin (tributylic glyceride) are so readily compatible with cellulose acetate whereas tricaproin is not. On the other hand, triacetin is soluble in water and and relatively volatile, and is, therefore, undesirable in cellulose actate coatings as a plasticizer, while tributyrin, which is insoluble in water, readily hydrolyzes to form butyric acid which on account or its bad odor is likewise objectionable.

Certain esters of dibasic acids, notably diethyl phthalate, dibutyltartrate or the ethylene glycol monoethyl ether diester o1 phthalic acid, are known to be compatible with cellulose acetate, but also possess certain disadvantages in the film due either to evaporation or hydrolysis. The esters of crotonic acid and monohydric aliphatic 5 alcohols of a boiling point sufliciently high to even be considered as possible plasticizers are, however, incompatible with cellulose acetate.

It was, therefore, quite surprising to find'that the aliphatic polyhydric alcohol esters of cro- 5o tonic acid as described herein when separated irom resinous impurities by distillation in vacuo are pale, thin, high-boiling oils, and are not only readily compatible with cellulose acetate, except as limited hereinafter, but possess other useiul physical properties. For example, they are unusually stable towards moisture or hydrolysis.

and possess an agreeable odor. In addition, they can be treated by the actionot heat and air, 1. e. they can be blown with air or oxygen-containing .0 gas at an elevated temperature (about -180" C.) to convert them into practically non-volatile viscous oils or solid rubber-like masses of pale color, which are likewise compatible with nitrocellulose or acetylcellulose, if the air-blowing is not carried too far, and which have unusually 5 good plastlcizing properties.

For the purpose of this invention, the purified vacuum-distilled polyhydric alcohol esters of crotonic acid are preferred, such as can be prepared, for example, by heating crotonic acid 10 (preferably in excess) with one of the group consisting of glycerol, pentaerythrite, triethylene glycol diethylene glycol HOCH2CH2OCH2CH2OH, trimethylene glycol OHCH2CH2CH2OH, ethylene glycol, and decamethylene glycol-1,10. Of these esters, those made from polyhydric aliphatic alcohols containing less than 7 carbon 20 atoms are compatible with either cellulose acetate or nitrocellulose, whereas those made from higher polyhydric alcohols, such as decamethylene glycol, are compatible with nitrocellulose but not with cellulose acetate. The heating is car- 25 ried out at a temperature of about -220 C. until the theoretical quantity of water has been split out by the esterification. A black more or less resinous mass is obtained which is useless unless suitably purified. The purification is car- 30 ried out by distilling directly in high vacuo whereby unchanged crotonic acid and partially esterified products come over first, followed by the substantially pure ester. Deleterious resinous by-products of dark color remain behind in 35 the still.

The properties of a few typical esters are as follows- Glycol dicrotonate (from ethylene glycol) -B. P.

120 0. at 3 mm.

Diethyleneglycol dicrotonate (from diethyleneglycol)-B. P. 146-l54 C. at 1 mm.

Triethyleneglycol dicrotonate (from triethyleneglycol)--B. P. 168-178 C. at 1 mm.

Glyceryl tricrotonate (from glycerol) -B. P. 170- 45 210 C. at 1-2 mm.

Pentaerythrite crotonate (from pentaerythrite)--B. P. 197-230 C. at 1-2 mm.

1,10-decamethyleneglycol dicrontonate (from LID-decamethylene glycoD-B. P. -187 c. 50 at 1 mm.

For use as plasticizers the above esters are mixed either with the cellulosic lacquer in solution, or, for molded plastics, are directly incor- 55 porated by kneading as is customary in the art; the quantity to be used depending upon the degree of plastification desired.

The air-blown esters are prepared by heating any of the above purified esters, either alone or go in admixture with each other, to a temperature of about bio-180 C. and passing a current of air or oxygen-containing gas through the liquid until the desired degree of bodying or increase in viscosity has occurred. This operation can be carried out in an inert organic solvent and catalysts to promote the oxidation can be added if desired, such as organic peroxides, or oxides and salts of heavy metals, particularly of cobalt, manganese, vanadium, and the like, which are known to have siccative properties in promoting oxidation of drying oils.

The purified croto-nic esters of the dihydricucts made by air-blowing the natural drying or semi-drying oils. The blown polycrotonates are thus film forming materials in themselves and can find application as resins in coating compositions of the most diverse nature. For special purposes the purified crotonates described herein can be admixed with natural or synthetic drying oils, semi-drying oils, autoxidizable resins and the like, and the mixture then blown with air at an elevated temperature to produce extremely tough condensation products which are useful in coating compositions, adhesives, and plastics.

Lacquers containing resinous cellulose derivatives, notably nitrocellulose orcellulose acetate,

plasticized with the polyhydric alcohol esters of crotonic acid of the type set forth herein, can be used on wood, metal, paper, leather, textile fabrics, artificial leather, or rubber to produce resistant coatings of good flexibility and adhesion. In general the weight ratio of plasticizer to cellulose derivative varies considerably with the surface and type of coating desired, and

can best be determined only by experiment. A 8

hydric alcohols which can be distilled in vacuum without decomposition and is meant to specifically exclude sugars or cellulose itself.

Although the vacuum distilled polyhydric alcohol esters of crotonic acid are good plasticizers for cellulosic derivatives, especially cellulose nitrate and acetate, they may also be used with 20 other organic plastic materials such as phenolformaldehyde resins and analogous brittle resins to toughen them.

This application is a division of copending application Serial No. 686,443, filed August 23, 26 1933.

It is understood that the above description is given by way of illustration only, and not of limitation, and that deviations are possible within the spirit of the invention, the scope of which 80 is limited only by the following claims.

What I claim is:

l. A crotonic acid ester of a polyhydric alcohol selected from the group consisting of glycerol, pentaerythrite, the glycols, and glycol ethers having two hydroxyl groups.

. Diethylene glycol dicrotonate.

. Polyethylene glycol dicrotonate.

. Glycerol tricrotonate.

. A crotonic acid ester of glycerol.

. Ethylene glycol dicrotonate.

. A crotonic acid ester of ethylene glycol.

HERMAN A. BRUSON. 

